TW202136349A - Hydroxy-terminated polyurethane prepolymer with low allophanate content - Google Patents

Abstract

The present invention relates to hydroxy-terminated polyurethane prepolymers that consist to an extent of at least 90% by weight of the product of the reaction of hexamethylene 1,6-diisocyanate with butane-1,4-diol and have an allophanate content of ≤ 1.00 mol%, to a process for the production thereof, to compositions comprising such polyurethane prepolymers and to the use of said polyurethane prepolymers.

Description

Hydroxyl-terminated polyurethane prepolymer with low allophanate content

The present invention relates to a hydroxyl-terminated polyurethane prepolymer, which is composed of at least 90% by weight of 1,6-hexamethylene diisocyanate and butane-1,4- The composition of the reaction product of the diol and the content of monourethane ≤ 1.00 mol% relates to a manufacturing method thereof, relates to a composition containing such a polyurethane prepolymer, and relates to a Use of polyurethane prepolymer.

Polyurethane prepolymer is an important component in polyurethane chemistry. Such as hydroxyl-terminated prepolymers, for example, they are used as OH components in combination with polyisocyanates in two-component coatings or adhesive systems. The basic application areas are adhesives used in the packaging industry or systems for coating leather or textiles (Kunststoff Handbuch [Plastics Handbook] volume 7, Polyurethane [Polyurethane], G. Oertel, Hanser Verlag, pp. 99 ff).

Thermoplastic aliphatic polyurethane prepolymers formed from short-chain aliphatic diols and aliphatic polyisocyanates have useful properties. Such as hard segment structural units, they are obviously suitable for the modification of a variety of products and materials. Compared to comparable thermoplastic polyurethane prepolymers with a higher allophanate content, thermoplastic polyurethane prepolymers with a low allophanate group content are particularly affected. Welcome, because urethanes reduce the crystallinity of the hard segment. In addition, urethanes cause branching, which reduces the fluidity of the polyurethane prepolymer.

JP4209619A and JP4309516A disclose thermoplastic polyurethane resin compositions with low urethane content. The polyurethanes have both hard and soft segments. The pure hard segment polyurethanes or polyurethane prepolymers are not described, especially those formed from aliphatic reactants alone.

JP2010001332A discloses an aqueous polyurethane resin dispersion with a low allophanate content. The polyurethanes have both hard and soft segments. The pure hard segment polyurethanes or polyurethane prepolymers are not described, especially those formed from aliphatic reactants alone.

The problem in the manufacture of aliphatic polyurethane prepolymers is that the high density of the reactive groups means that the polyaddition reaction of short-chain aliphatic diols and aliphatic polyisocyanates has a high heat of reaction. / Enthalpy, if it is not sufficiently dissipated, it will cause damage, such as discoloration, depending on the reformation of the monomer and the destruction (ashing) of the polyurethane prepolymer. The increased reaction temperature also catalyzes the undesired allophanate formation reaction. This produces branched and crosslinked polymers.

In industrial implementation, priority is given to continuous manufacturing methods because they make it easy to expand the manufacturing scale and allow the desire to produce larger quantities with a fixed amount. The use of solvents is also disadvantageous because the residual solvents left in the product will be released into its surrounding environment, causing undesirable properties such as odor, toxicity and/or deterioration of mechanical properties. The complete removal of residual solvent from the polymer is essentially related to technical complexity and energy consumption.

DE 10 2011 085 944 A1 describes a method for producing low-melting thermoplastic polyurethane in a loop reactor. The high reaction temperature required for this method promotes the formation of the allophanate and makes it difficult or impossible to dissipate the heat released in the highly exothermic reaction.

For example, WO01/14441 discloses a method for manufacturing polyurethane. This reveals a method for making NCO-, NH- or OH-terminated polyurethanes in a static mixer. The key to this method is that the temperature during the reaction of the ingredients is controlled adiabatically and/or that the static mixer is slightly heated, so it is only suitable for methods that endothermic or have only low exothermicity. This method is not suitable for the reaction of components with high reaction enthalpy, that is, components that react together strongly exothermic.

The disadvantages of the above-mentioned methods are that they are mainly suitable for endothermic or reactions with only low heat of reaction, and therefore require a fixed heat input or must be adiabatic controlled. In a system with high reaction exotherm (≤ -350 kJ/kg), adiabatic temperature rise is problematic. Starting from the monomer at a temperature sufficient for the initiation of the non-catalytic reaction (>50°C), the temperature of the reaction product in adiabatic mode will rise to much higher than 300°C. Due to a large number of thermal side reactions, the production and processing of polyurethanes at a temperature of> 200°C for a long time is problematic. The temperature of 300°C is even higher than the upper limit temperature of the polyurethane bond. The upper limit temperature is defined as the temperature at which the depolymerization reaction is in equilibrium with the polymerization reaction.

One object of the present invention is to provide a hydroxyl-terminated polyurethane prepolymer which is formed by at least 90% by weight of aliphatic structural units and has a comparable aliphatic polyurethane prepolymer. The polymer has a lower allophanate content, and a method for its production.

This objective is achieved by a hydroxyl-terminated polyurethane prepolymer, which is characterized in that the hydroxyl-terminated polyurethane prepolymer is composed of at least 90% by weight of 1,6 -The composition of the reaction product of hexamethylene diisocyanate and butane-1,4-diol, based on the total mass of the hydroxyl-terminated polyurethane prepolymer, and lies in the hydroxyl-terminated polyurethane prepolymer The allophanate content of the terminal polyurethane prepolymer is ≤ 1.00 mol% so that all the urethane and allophanate groups in the hydroxyl-terminated polyurethane prepolymer The sum of the clusters is used as a reference, and is measured by NMR spectroscopy in each case.

It was surprisingly found that the hydroxy-terminated prepolymer of the present invention has a significantly lower urethane content than comparable hydroxy-terminated polyurethane prepolymers prepared by common batch methods. This low allophanate content causes an insignificant decrease in the crystallinity of the hard segment. The low urethane content also causes smaller branching, which reduces the fluidity of the polyurethane prepolymer.

In the context of the present invention, the word "一(a)" associated with a countable parameter is understood to mean the number "one" only when the number is clearly stated (for example, it means "exactly one"). When referring to, for example, "one (a) polyol" below, the word "one (a)" is understood to mean only the indefinite article and not the number "one"; a mixture containing at least two glycols The specific implementation is therefore also covered.

According to the present invention, the term "comprising" or "containing" preferably means "essentially composed of" and more preferably means "consisting of".

The allophanate concentration was measured by ¹ H NMR spectroscopy (Instrument: Bruker AV III HD 600, at a measurement frequency of 600.36 MHz, using the zg30 pulse program, with 64 scans, 6 s relaxation delay (D1) and TE of 354 K). In response, the polyurethane prepolymer sample was dissolved in deuterated dimethyl sulfide (DMSO-d ₆ ) at 80° C. and then measured. Use MestReNova software to evaluate spectra. First, apply a baseline correction (Whittaker leveler), which then integrates the CH _{2 based allophanate-specific protons between 3.56 ppm and 3.66 ppm and the O-CH 2} between 3.84 ppm and 4.04 ppm Carbamate-specific protons. The sum of the two integrals is then calculated and used to determine the percentage ratio of the allophanate signal, which corresponds to the molar ratio of the allophanate group.

，質量-平均莫耳質量

及數目-平均莫耳質量

藉凝膠滲透層析法(GPC)使用聚甲基丙烯酸甲酯作為標準品測定。將待分析樣品溶解於一3 g的三氟乙酸鉀於400立方公分的六氟異丙醇之溶液中(樣品濃度約2 mg/立方公分)，然後經由一預-管柱於一1立方公分/分鐘的流速下施用及之後藉由三個串連的層析管柱方式來分離，首先藉由一1000 Å PSS PFG 7 µm層析管柱方式，然後藉由一300 Å PSS PFG 7 µm層析管柱方式及最後藉由一100 Å PSS PFG 7 µm層析管柱方式。所用的檢測器為一折射率檢測器(RI檢測器)。Unless explicitly stated otherwise, in the present invention, centrifugation-average molar mass

, Quality-average molar mass

And number-average molar mass

It was determined by gel permeation chromatography (GPC) using polymethyl methacrylate as a standard. Dissolve the sample to be analyzed in a solution of 3 g of potassium trifluoroacetate in 400 cm3 of hexafluoroisopropanol (the sample concentration is about 2 mg/cm3), and then pass through a pre-column to 1 cm3 It is applied at a flow rate of 1/min and then separated by three series of chromatography columns, first by a 1000 Å PSS PFG 7 µm column method, and then by a 300 Å PSS PFG 7 µm layer Analytical column method and finally a 100 Å PSS PFG 7 µm chromatography column method. The detector used is a refractive index detector (RI detector).

)是借助下列方程式由藉該凝膠滲透層析法量測所獲得的數據計算得的：

以g/mol 式中：

是該分部

的聚合物的莫耳質量，如此致對全部

的

，以g/mol，

是該分部

的聚合物的莫耳量，以mol。The centrifugation-average molar mass (

) Is calculated from the data obtained by the gel permeation chromatography measurement with the aid of the following equation:

In g/mol formula:

Is the branch

The molar mass of the polymer, so to all

of

, In g/mol,

Is the branch

The molar amount of the polymer in mol.

)是借助下列方程式同樣由藉該凝膠滲透層析法量測所獲得的數據計算得的：

以g/mol 式中：

是該分部

的聚合物的莫耳質量，如此致對全部

的

，以g/mol，

是該分部

的聚合物的莫耳量，以mol。The mass-the average molar mass (

) Is also calculated from the data obtained by the gel permeation chromatography measurement with the aid of the following equation:

In g/mol formula:

Is the branch

The molar mass of the polymer, so to all

of

, In g/mol,

Is the branch

The molar amount of the polymer in mol.

)是借助下列方程式同樣由藉該凝膠滲透層析法量測所獲得的數據計算得的：

以g/mol 式中：

是該分部

的聚合物的莫耳質量，如此致對全部

的

，以g/mol，

是該分部

的聚合物的莫耳量，以mol。The number-the average molar mass (

) Is also calculated from the data obtained by the gel permeation chromatography measurement with the aid of the following equation:

In g/mol formula:

Is the branch

The molar mass of the polymer, so to all

of

, In g/mol,

Is the branch

The molar amount of the polymer in mol.

Unless specifically stated otherwise, the melting point is determined by DSC (Differential Scanning Calorimetry) according to DIN-EN-ISO 11357-1 using a DSC 8500 (PerkinElmer, USA). Calibration is performed by the melting start temperature of octane, indium, lead and zinc. Weigh approximately 10 mg of material into an aluminum crucible. The measurement was performed by two heating strokes from -20°C to +210°C at a heating rate of 20 K/min and subsequent cooling at a cooling rate of 20 K/min. Use compressor cooler for cooling. The purge gas used was nitrogen. Each value is recorded based on the evaluation of the 2nd heating curve.

A preferred embodiment relates to a hydroxyl-terminated polyurethane preform obtained or obtainable by the reaction of at least 1,6-hexamethylene diisocyanate and butane-1,4-diol. Polymer, optionally in the presence of a catalyst and/or additives and additives, the molar NCO/OH ratio is in the range from 0.6:1.0 to 0.95:1.0, the reaction is preferably a loop reaction Or in a static mixer, the loop reactor or static mixer preferably has at least one heat transfer unit for continuous conduction of heat, and the conduction of heat preferably totals from 10% to 90%, more preferably From 20% to 70%, particularly preferably from 25% to 60%, the total reaction enthalpy released in the tubular reactor is characterized in that the hydroxyl-terminated polyurethane prepolymer is to a certain extent It is composed of at least 90% by weight of the reaction product of 1,6-hexamethylene diisocyanate and butane-1,4-diol, and the total amount of the hydroxyl-terminated polyurethane prepolymer The quality is the basis, and the allophanate content of the hydroxyl-terminated polyurethane prepolymer is ≤ 1.00 mol% so that all the amine groups in the hydroxyl-terminated polyurethane prepolymer The sum of the formate and allophanate groups is used as a reference, and is determined by NMR spectroscopy in each case.

In a preferred embodiment, the hydroxyl-terminated polyurethane prepolymer is prepared by a continuous process, especially the at least 1,6-hexamethylene diisocyanate and butane-1 The reaction of 4-diol is carried out in a loop reactor or in a static mixer.

A preferred embodiment relates to a hydroxyl-terminated polyurethane preform obtained or obtainable by the reaction of at least 1,6-hexamethylene diisocyanate and butane-1,4-diol. The polymer, optionally in the presence of a catalyst and/or additives and additives, the molar NCO/OH ratio is in a range from 0.6:1.0 to 0.95:1.0, and a method includes the steps: a) Manufacture a mixture of part of hexamethylene diisocyanate (HDI) and all butanediol (BDO); b) mixing the mixture obtained in method step a) with a partial output stream of oligomers obtained in method step e); c) allowing the mixture from process step b) to react; d) dividing the reaction mixture obtained in step c) into two partial output streams; e) taking a part of the output stream from method step d) as a part of the input stream of the mixture in method step b); f) Discharging the remaining part of the output stream containing the hydroxyl-terminated polyurethane prepolymer from step d) of the method, characterized in that the hydroxyl-terminated polyurethane prepolymer is at a certain level The above is composed of at least 90% by weight of the reaction product of 1,6-hexamethylene diisocyanate and butane-1,4-diol, and the hydroxyl-terminated polyurethane prepolymer Based on the total mass, and the allophanate content of the hydroxyl-terminated polyurethane prepolymer is ≤ 1.00 mol% so that all amines in the hydroxyl-terminated polyurethane prepolymer The sum of the carbamate and allophanate groups is used as a reference, and is determined by NMR spectroscopy in each case.

In a preferred embodiment, the hydroxyl-terminated polyurethane prepolymer is prepared by a continuous process, especially at least 1,6-hexamethylene diisocyanate and butane-1, The reaction of 4-diol is carried out in a loop reactor, the loop reactor has at least one heat transfer unit that continuously conducts the heat away, and the heat conduction away preferably totals from 10% to 90%, more preferably from 20%. % To 70%, particularly preferably from 25% to 60%, the total reaction enthalpy released in the loop reactor.

A further object of the present invention relates to a hydroxyl-terminated polyurethane obtained or obtainable by the reaction of at least 1,6-hexamethylene diisocyanate and butane-1,4-diol Prepolymer, optionally in the presence of a catalyst and/or additives and additives, a method comprising the steps: a) Mix a polyisocyanate stream (A) and a polyol stream (B) in a first mixing unit (7) to obtain a mixed stream (C), adjust the polyisocyanate stream (A) and a polyol stream The mass flow rate of (B) is such that the molar ratio of the isocyanate to the hydroxyl group in the mixed stream (C) is in the range from 0.6:1.0 to 0.95:1.0, b) The mixed stream (C) is introduced into a circulating circulating stream (D), wherein the monomers of the polyisocyanate stream (A) and the polyol stream (B) are further reacted in the circulating stream (D) to To form a prepolymer, preferably a hydroxyl terminated prepolymer, c) turning a substream of the circulating stream (D) into a prepolymerized stream (E) containing the thermoplastic aliphatic polyurethane prepolymer, d) Selectively squeeze the prepolymer stream (E), It is characterized in that the hydroxyl-terminated polyurethane prepolymer is composed of at least 90% by weight of 1,6-hexamethylene diisocyanate and butane-1,4-diol. The composition of the reaction product is based on the total mass of the hydroxyl-terminated polyurethane prepolymer, and the urethane content of the hydroxyl-terminated polyurethane prepolymer is ≤ 1.00 mol% Measured by NMR spectroscopy in each case based on the sum of all urethane and allophanate groups in the hydroxyl-terminated polyurethane prepolymer.

In a preferred embodiment, the hydroxyl-terminated polyurethane prepolymer is prepared by a continuous process, especially at least 1,6-hexamethylene diisocyanate and butane-1, The reaction of 4-diol is carried out in a loop reactor, the loop reactor has at least one heat transfer unit that continuously conducts the heat away, and the heat conduction away preferably totals from 10% to 90%, more preferably from 20%. % To 70%, particularly preferably from 25% to 60%, the total reaction enthalpy released in the loop reactor.

為於一自1.5至19的範圍內，較佳於一自2至9的範圍內及更佳於一自3.2至6的範圍內，該平均聚合度為

，在此

是在該多異氰酸酯單體中的NCO基團對在該多醇單體中的羥基基團之比例，特別是在此

是在所用的多異氰酸酯單體中的NCO基團對在所用的多醇單體中的羥基基團之比例。In a preferred embodiment, the average degree of polymerization of the hydroxyl-terminated polyurethane prepolymer of the present invention is

To be in a range from 1.5 to 19, preferably in a range from 2 to 9 and more preferably in a range from 3.2 to 6, the average degree of polymerization is

,here

Is the ratio of the NCO groups in the polyisocyanate monomer to the hydroxyl groups in the polyol monomer, especially here

It is the ratio of the NCO groups in the polyisocyanate monomer used to the hydroxyl groups in the polyol monomer used.

The aliphatic polyisocyanate monomer used is preferably 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanate Hexane (HDI) or a mixture of at least two of these, more preferably 1,6-diisocyanatohexane (HDI).

The aliphatic polyol monomer used is preferably propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol and/or a mixture of at least two of these, More preferably butane-1,4-diol. Preference is given to using unbranched polyol monomers.

In a preferred embodiment, the hydroxyl-terminated polyurethane prepolymer of the present invention is at least 96% by weight to a certain extent, preferably at least 97% by weight, and more preferably to a certain extent. From at least 98% by weight, even more preferably from at least 99% by weight to a certain extent, even more preferably from at least 99.5% by weight to a certain extent, and most preferably from at least 99.9% by weight of 1,6-di The composition of the reaction product of hexamethylene isocyanate and butane-1,4-diol is based on the total mass of the hydroxyl-terminated polyurethane prepolymer. When determining the ratio of the reaction product of 1,6-hexamethylene diisocyanate and butane-1,4-diol, only the polymerizable composition is considered, and the polymerizable thermoplastic aliphatic polyamine group The total mass of the formate prepolymer is the benchmark.

In a preferred embodiment, the urethane content of the hydroxyl-terminated polyurethane prepolymer of the present invention is in the range of from 0.25 mol% to 1.00 mol%, preferably from 0.25 mol%. mol% to 0.80 mol%, more preferably a range from 0.30 mol% to 0.80 mol%, even more preferably a range from 0.30 mol% to 0.75 mol%, even more preferably a range from 0.30 mol% to 0.75 mol% Within the range of 0.34 mol% to 0.70 mol%, based on the sum of all urethane and allophanate groups in the hydroxyl-terminated polyurethane prepolymer, by NMR spectroscopy Determination.

In a preferred embodiment, the thermoplastic aliphatic polyurethane prepolymer of the present invention has an average OH functionality, calculated from the functionality of the monomer, ranging from 1.8 to 2.1, preferably 1.95 To 2.05, more preferably 1.97 to 2.0, most preferably 1.975 to 2.0.

/

為於一自2至20的範圍內，較佳於一自2.5至15的範圍內，更佳於一自4至10的範圍內，在此

是該數目-平均莫耳質量及

是該質量-平均莫耳質量，在各情況下藉凝膠滲透層析法，將該樣品溶解在具有濃度為2 mg/cm³ 的三氟乙酸鉀於六氟異丙醇的溶液中及使用聚甲基丙烯酸甲酯標準品所測定。In a preferred embodiment, the proportion of the hydroxyl-terminated polyurethane prepolymer of the present invention is

/

It is in a range from 2 to 20, preferably in a range from 2.5 to 15, more preferably in a range from 4 to 10, where

Is the number-the average molar mass and

It is the mass-the average molar mass. In each case, by gel permeation chromatography, the sample is dissolved in a solution of ^{potassium trifluoroacetate with a concentration of 2 mg/cm 3} in hexafluoroisopropanol and used Measured by polymethyl methacrylate standards.

/

為於一自2.3至5的範圍內， 較佳於一2.3至4的範圍內，在此

是該離心-平均莫耳質量及

是該質量-平均莫耳質量，在各情況下藉凝膠滲透層析法，將該樣品溶解於一具有濃度為2 mg/cm³ 的三氟乙酸鉀於六氟異丙醇的溶液中及使用一聚甲基丙烯酸甲酯標準品，測定。In a further preferred embodiment, the proportion of the hydroxyl-terminated polyurethane prepolymer of the present invention is

/

Is in a range from 2.3 to 5, preferably in a range from 2.3 to 4, where

Is the centrifugation-average molar mass and

It is the mass-the average molar mass. In each case, by gel permeation chromatography, the sample is dissolved in a solution of ^{potassium trifluoroacetate with a concentration of 2 mg/cm 3} in hexafluoroisopropanol and Use a polymethyl methacrylate standard for determination.

In a further preferred embodiment, the hydroxy-terminated polyurethane prepolymer of the present invention has a melting point of> 150°C, preferably a melting point of> 160°C, more preferably a melting point of 165°C The melting point in the range of 190°C is determined by differential scanning calorimetry in accordance with DIN EN 61006 (November 2004).

A further object of the present invention relates to a method for producing the hydroxyl-terminated polyurethane prepolymer of the present invention, which is characterized in that at least 1,6-hexamethylene diisocyanate and butane-1,4 -Diol reaction, optionally in the presence of a catalyst and/or additives and additives, the molar NCO/OH ratio is in the range from 0.6:1.0 to 0.95:1.0.

In addition to hexamethylene 1,6-diisocyanate, one or more other polyisocyanates can be used, such as aromatic polyisocyanates, cycloaliphatic polyisocyanates and/or araliphatic polyisocyanates . More specifically, in addition to hexamethylene 1,6-diisocyanate, one or more aliphatic polyisocyanates other than hexamethylene 1,6-diisocyanate are used.

Suitable aliphatic polyisocyanates are all aliphatic polyisocyanates known to those skilled in the art, especially monomeric aliphatic diisocyanates. Suitable compounds are preferably in the molecular weight range from ≥ 140 g/mol to ≤ 400 g/mol, regardless of whether they have been obtained by phosgene or phosgene-free methods. The polyisocyanates and/or their precursor compounds may have been obtained from fossil or biological sources. Preference is given to hexamethylene-1,6-diamine and 1,5-diisocyanatopentane from pentamethylene-1,5-diamine, and hexamethylene that has been obtained from biological sources. Methyl-1,6-diamine and pentamethylene-1,5-diamine are used to prepare 1,6-diisocyanatohexane (HDI), preferably by bacterial fermentation.

Examples of suitable aliphatic diisocyanates are 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane ( HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4 ,4-Trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane and 1,10-diisocyanatodecane.

In the context of the present invention, the term "monomeric diisocyanate" is understood to mean a diisocyanate that does not include dimers, trimers, etc., and is a part of dimers, trimers, and other structures, and/or An NCO group and an NCO-reactive group (e.g., urethane, urea, carbodiimide, urea, amide, isocyanurate, allophanate, biuret, oxalate, etc.) Diazine trione, uret dione and/or imino oxadiazine dione structure) reaction product.

In a preferred embodiment, the one or more aliphatic polyisocyanates used in addition to 1,6-diisocyanate hexamethylene ester are selected from 1,4-diisocyanatobutane, 1 ,5-Diisocyanatopentane, 2-methyl-1,5-diisocyanatopentane, and/or a group consisting of a mixture of at least two of these. In another preferred embodiment, 1,5-diisocyanatopentane and/or 1,6-diisocyanatohexane are used as aliphatic polyisocyanates. In a further preferred embodiment, 1,6-diisocyanatohexane is used alone.

In addition to butane-1,4-diol, one or more other polyols can be used. More specifically, in addition to butane-1,4-diol, other than butane-1,4-diol and having a molecular weight in the range from 62 g/mol to 210 g/mol can be used. Preferably, one or more aliphatic polyols ranging from 62 g/mol to 120 g/mol.

Suitable as other aliphatic polyols are all organic diols with a molecular weight in the range of from 62 g/mol to 210 g/mol known to those skilled in the art, preferably having a molecular weight of from 62 g/mol to 210 g/mol. Diols in the range of g/mol to 120 g/mol. The glycols and/or their precursor compounds may have been obtained from fossil or biological sources. The aliphatic diols used to form the thermoplastic polyurethane polymer of the present invention are preferably selected from ethane-1,2-diol, propane-1,2-diol, propane-1,3 -Diol, butane-1,2-diol, butane-1,3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4 -Diol, pentane-1,5-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5 -Diol, hexane-1,6-diol, or a group consisting of a mixture of at least two of these. It is preferred to use unbranched aliphatic diols.

In a preferred embodiment, other aliphatic diols are selected from ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1, 2-diol, butane-1,3-diol, pentane-1,5-diol, hexane-1,6-diol, and/or a group consisting of a mixture of at least two of these. In a further preferred embodiment, propane-1,3-diol, hexane-1,6-diol and/or mixtures thereof are used as other aliphatic diols. In another preferred embodiment, butane-1,4-diol is used alone as the aliphatic diol.

The reaction to form the co-reactant of the thermoplastic aliphatic polyurethane prepolymer of the present invention can occur in the presence of one or more catalysts.

Suitable catalysts according to the present invention are conventional tertiary amines known in the prior art, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(Dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, etc., and especially organometallic compounds such as titanium esters, iron compounds, tin compounds, eg tin diacetate , Tin dioctanoate, tin dilaurate or dialkyl tin salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate and so on. Preferred catalysts are organometallic compounds, especially titanium esters, iron compounds and/or tin compounds.

The amount of the catalyst is 0.001% to 2.0% by weight, preferably 0.005% to 1.0% by weight, more preferably 0.01% to 0.1% by weight, based on the diisocyanate component. The catalyst can be used in pure form or dissolved in the glycol component. This has the advantage that as a result of the additional use of any catalyst solvent, the resulting thermoplastic polyurethanes do not contain any impurities. The catalyst can be added in one or more parts or continuously, for example by means of a suitable metering pump, during the entire reaction period.

Alternatively, it is also possible to use the catalyst (set) and a catalyst solvent, preferably a mixture with an organic catalyst solvent. The dilution of the catalyst solution can be freely selected in a wide range. The catalytically active solutions are those with a concentration of 0.001% by weight and above.

Suitable solvents for the catalyst are, for example, solvents that are inert to isocyanate groups, such as hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether , Dipropylene glycol dimethyl ether, ethylene glycol monomethyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol monomethyl acetate Base ether ester, 1-methoxy-2-propyl acetate, 3-methoxy-n-butyl acetate, propylene glycol diacetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone, lactones, such as β-propiolactone, γ-butyrolactone, ε-caprolactone and ε-methylcaprolactone, and solvents such as N-methylpyrrolidone and N- Methyl caprolactam, 1,2-propyl carbonate, dichloromethane, dimethyl sulfenium, triethyl phosphate, or any desired mixture of such solvents.

Alternatively, a solvent that is reactive with isocyanates and can be incorporated into the diisocyanate can be used for the catalyst. Examples of such solvents are mono- and polybasic simple alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2-ethyl-1-hexanol, ethylenedi Alcohol, propylene glycol, the isomeric butanediols, 2-ethylhexane-1,3-diol or glycerol; ether alcohols, such as 1-methoxy-2-propanol, 3- Ethyl-3-hydroxymethyloxetane, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Base ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol or liquid higher molecular weight polyethylene glycols, polypropylene glycols, mixed polyethylene glycols /Polypropylene glycol and its monoalkyl ethers; ester alcohols, such as ethylene glycol monoacetate, propylene glycol monolaurate, glycerol mono- and diacetate, glycerol monobutyrate or monoisobutyl Acid 2,2,4-trimethylpentane-1,3-diol ester; unsaturated alcohols, such as allyl alcohol, 1,1-dimethylallyl alcohol or oleyl alcohol; aromatic fat Group alcohols, such as benzyl alcohol; N-monosubstituted amides, such as N-methylformamide, N-methylacetamide, cyanoacetamide or 2-pyrrolidone, or the like Any desired mixture of solvents.

The auxiliaries and additives used can be, for example, standard auxiliaries and additives in the field of thermoplastic technology, such as dyes, fillers, processing aids, plasticizers, nucleating agents, stabilizers, flame retardants, mold release agents or Strengthening aids and additives. Other details on the mentioned auxiliaries and additives can be found in professional literature, such as in the monograph "High Polymers", volume XVI, Polyurethane [Polyurethanes], parts 1 and 2, Interscience by JH Saunders and KC Frisch Publishers 1962 and 1964, in "Taschenbuch für Kunststoff-Additive" [Plastics Additives Handbook] (Hanser Verlag Munich 1990) by R. Gächter and H. Müller or in DE-A 29 01 774. It is self-evident that it is also advantageous to use multiple types of auxiliaries and additives.

The process of the invention can be carried out in a loop reactor or in a mixer, for example in a static mixer. The method of the present invention can preferably be carried out in a loop reactor. The method of the present invention is preferably a continuous method.

The thermoplastic aliphatic polyurethane prepolymer of the present invention obtained or obtainable by the method of the present invention may additionally contain unreacted monomers or otherwise be present in the product of the method. This occurs, for example, when a monomer (such as the diol component) is used in excess. The amount of unreacted monomer is preferably within a range from 0.05% by weight to 12% by weight, more preferably within a range from 0.35% by weight to 9% by weight, particularly preferably from 0.75% by weight to 6% by weight. Within the range, in each case, the total mass of the composition is used as the reference.

In a preferred embodiment of the method of the present invention, the reaction is carried out in a tubular reactor, preferably in a loop reactor or in a static mixer, the tubular reactor having at least one continuous separation A thermal heat transfer unit, the heat conducted away preferably totals from 10% to 90%, more preferably from 20% to 70%, particularly preferably from 25% to 60%, which should be released in the tubular reactor Total reaction enthalpy.

In a preferred embodiment of the method of the present invention, the method is solvent-free.

In a preferred embodiment of the method of the present invention, the method is a continuous method.

A further object of the present invention relates to a composition comprising at least one hydroxyl-terminated polyurethane prepolymer of the present invention and at least one polyol, preferably diol, more preferably butanediol, particularly preferably Butane-1,4-diol.

A preferred embodiment of the present invention relates to a composition comprising at least one hydroxy-terminated polyurethane prepolymer of the present invention and butane-1,4-diol, and the butane in the composition The amount of -1,4-diol is preferably within a range from 0.05% by weight to 12% by weight, more preferably within a range from 0.35% by weight to 9% by weight, particularly preferably within a range from 0.75% by weight to 6 Within the range of% by weight, the total mass of the composition is used as a reference in each case.

A further preferred embodiment of the present invention relates to a composition comprising at least one hydroxyl-terminated polyurethane prepolymer of the present invention and at least one additive. All the additives and auxiliaries mentioned above are suitable as additives.

A further object of the present invention relates to a hydroxyl-terminated polyurethane prepolymer of the present invention or the composition of the present invention for the production of thermoplastic polyurethane and/or thermoplastic polyurethane The use of dispersion, especially for the manufacture of thermoplastic polyurethane.

A further object of the present invention relates to a polymer obtainable by the reaction of at least one hydroxyl-terminated polyurethane prepolymer of the present invention or the composition of the present invention with at least one chain extender. The extender is preferably a polyisocyanate.

The hydroxyl-terminated polyurethane prepolymer of the present invention or the composition of the present invention is preferably reacted with at least one chain extender to form a polyurethane polymer. When a polyisocyanate is used as a chain extender, all polyisocyanates known to those skilled in the art are suitable, preferably aliphatic polyisocyanates, aromatic polyisocyanates, cycloaliphatic polyisocyanates, and Aromatic polyisocyanates. The reaction between the prepolymer to be formed into the polymer and the chain extender can be carried out, for example, in an extruder.

A further object of the present invention relates to an article containing or containing a polymer of the present invention, a hydroxy-terminated polyurethane prepolymer of the present invention or a composition of the present invention.

A further object of the present invention relates to the use of a polymer of the present invention for the production of shaped bodies, films and/or fibers.

Example

The present invention is further illustrated by the following embodiments, but is not limited thereto.

Color value

The color value in the CIE-Lab colour space is measured according to DIN EN ISO 11664-1 (July 2011) using a Konica Minolta CM 2600d spectrophotometer with D 65 light source and 10° observer.

Allophanate content

The concentration of allophanate was determined by ¹ H NMR spectroscopy (Instrument: Bruker AV III HD 600, at a measurement frequency of 600.36 MHz, using the zg30 pulse program, with 64 scans, 6 s relaxation delay (D1) and 354 TE of K). In response, the polyurethane prepolymer sample was dissolved in deuterated dimethyl sulfide (DMSO-d ₆ ) at 80° C. and then measured. Use MestReNova software to evaluate spectra. First, apply a baseline correction (Whittaker leveler), which then integrates between 3.56 ppm to 3.66 ppm of CH ₂ based allophanate-specific protons and between 3.84 ppm to 4.04 ppmnd of O-CH ₂ based Carbamate-specific proton. The sum of the two integrals is then calculated and used to determine the percentage ratio of the allophanate signal, which corresponds to the molar ratio of the allophanate group.

Gel permeation chromatography:

The molar mass of the polymer was determined by gel permeation chromatography (GPC). For this purpose, the sample to be analyzed is dissolved in a solution of 3 g of potassium trifluoroacetate in 400 cm3 of hexafluoroisopropanol (the sample concentration is about 2 mg/cm3). Each GPC uses the following components to measure at a flow rate of 1 cm³/min: Pump: 515 HPLC pump (Waters GmbH) Detector: Smartline 2300 RI detector (Knauer Wissenschaftliche Geräte GmbH) String: 1 Pre-column, in the order specified 1000 Å PSS PFG 7 µm, 300 Å PSS PFG 7 µm, 100 Å PSS PFG 7 µm Degassing: PSS degasser (Polymer Standards Service GmbH) Injection volume: 100 μl temperature: 23 to 25°C Mole quality standard: Polymethyl methacrylate standard set (PSS Polymer Standards Service GmbH)

及

及

之計算：

and

and

Calculation:

)是借助下列方程式由藉該凝膠滲透層析法量測所獲得的數據計算得的：

以g/mol 式中：

是該分部

的聚合物的莫耳質量，如此致對全部

的

，以g/mol，

是該分部

的聚合物的莫耳量，以mol。The centrifugation-average molar mass (

) Is calculated from the data obtained by the gel permeation chromatography measurement with the aid of the following equation:

In g/mol formula:

Is the branch

The molar mass of the polymer, so to all

of

, In g/mol,

Is the branch

The molar amount of the polymer in mol.

)是借助下列方程式同樣由藉該凝膠滲透層析法量測所得的數據計算得的：

以g/mol 式中：

是該分部

的聚合物的莫耳質量，如此致對全部

的

，以g/mol，

是該分部

的聚合物的莫耳量，以mol。The mass-the average molar mass (

) Is also calculated from the data measured by the gel permeation chromatography method with the aid of the following equation:

In g/mol formula:

Is the branch

The molar mass of the polymer, so to all

of

, In g/mol,

Is the branch

The molar amount of the polymer in mol.

)是借助下列方程式同樣由藉該凝膠滲透層析法量測所獲得的數據計算得的：

以g/mol 式中：

是該分部

的聚合物的莫耳質量，如此致對全部

的

，以g/mol，

是該分部

的聚合物的莫耳量，以mol。The number-the average molar mass (

) Is also calculated from the data obtained by the gel permeation chromatography measurement with the aid of the following equation:

In g/mol formula:

Is the branch

The molar mass of the polymer, so to all

of

, In g/mol,

Is the branch

The molar amount of the polymer in mol.

Differential Scanning Calorimetry (DSC)

The melting point is determined by DSC (differential scanning calorimetry) according to DIN-EN-ISO 11357-1 using a DSC 8500 (PerkinElmer, USA). Calibration is performed by the melting start temperature of octane, indium, lead and zinc. Weigh approximately 10 mg of material into an aluminum crucible. The measurement is performed by two heating strokes from -20°C to +210°C at a heating rate of 20 K/min and subsequent cooling at a cooling rate of 20 K/min. Cooling takes place by means of a compressor cooler. The purge gas used was nitrogen. Each value is recorded based on the evaluation of the 2nd heating curve.

I. Raw materials used

Hexamethylene 1,6-diisocyanate (HDI, purity ≥99% by weight) was obtained from Covestro Deutschland AG.

Butane-1,4-diol (BDO, purity ≥99% by weight) was obtained from Ashland.

Example 1

1,6-Hexamethylene diisocyanate (HDI) is transported from a storage tank to a static mixer (stream A) by a pump at room temperature. The butane-1,4-diol (BDO) heated to about 40°C is also transported by a pump from another storage tank to the continuous mixer (stream B). The fluxes of the HDI stream A and the BDO stream B are monitored by mass flow meters. In the mixer 7, the HDI stream A and the BDO stream B are mixed/dispersed to form an HDI/BDO dispersion (stream C).

The HDI/BDO stream C is combined and mixed with a prepolymerized stream D heated to 182°C to be recycled in a mixer (stream E). The temperature of the prepolymer stream D causes a reaction between HDI and BDO, which is maintained by further mixing in a temperature-controllable mixer, the formation of the prepolymer and the dissipation of the reaction heat. The temperature-controllable mixer uses heat transfer oil for heating/cooling and has a heat exchange surface area of at least 0.31 m ² . The inflow temperature of the heating medium is about 180°C. The output stream obtained from the temperature-controllable mixer is in the form of a prepolymerized HDI/BDO stream with a large number of reactions at a temperature of 183°C (stream E). The temperature-controllable static mixer is similar in structure to the Sulzer SMX reactor with internal cross-tubes. It has an internal volume of 2.2 liters and a heat exchange surface area of 0.31 square meters. Under operating conditions, its heat exchange capacity is 78 watts per Kelvin based on the product side. Based on the total volume of the 4 liter loop reactor, the heat transfer coefficient is 19 kilowatts per cubic meter and Kjeldahl temperature. The heat conducted away by the heat transfer unit is about 890 watts. The ratio of heat transfer surface area to total surface area is 0.655. The average OH functionality is exactly 2. At a branch point, the stream E is divided into two sub-streams F and G. The sub-stream F is fed back into the mixer by a pump as the prepolymerized stream D, and is heated to about 182°C through the pipeline. The mass flow rate of flow G corresponds to the mass flow rate of flow C. The mass flow rate of this stream G is approximately 115 L/h. The substream G is collected in a 60 L bucket and cooled. The resulting product is crystalline and white. The total amount of prepared prepolymer was 50 kg. The number of color fingers measured an L value of 92.2, an a value of 0.7 and a b value of 1.7. The viscosity of the product is 0.7 Pa s at 190°C.

In the embodiment of the present invention, the following reactant streams are used: kg/h mol/h Stream A HDI 4.367 25.965 Stream B BDO 3.000 33.289

。聚合度為

。The ratio of the NCO groups in the polyisocyanate monomer to the hydroxyl groups in the polyol monomer is

. The degree of polymerization is

.

It was determined that the allophanate content was 0.34%.

The average functionality of this monomer is 2.

為10810 g/mol，

為1404 g/mol，因此該比例為7.7。

為28940 g/mol及該比例

=2.68。Measured

Is 10810 g/mol,

It is 1404 g/mol, so the ratio is 7.7.

28940 g/mol and the ratio

= 2.68.

The melting point is 175.5°C.

The heat dissipated in the tubular reactor is approximately 57% of the total reaction enthalpy released therein.

Example 2 :

1.49 kg/h of HDI is transported from storage tank 1 to mixer 1 by means of a pump 1 (mzr-7255 ring gear pump from HNP). At the same time, 2.00 kg/h of BDO was transported from storage tank 2 to the same mixer by means of a pump 2 (mzr-7205 from HNP). The two material streams are mixed in the mixer at room temperature. The mixer used was a Sulzer SMX with a diameter of 6 mm and the ratio of length to diameter L/D = 10. This mixture is then fed into the reactor 1, which has been heated to 150°C (model: CSE-X/8G, Form G, inner diameter = 21.0 mm, length = 1000 mm, available from Fluitec). The resulting prepolymer with a HDI:BDO ratio of 0.4:1.0 is then combined in mixer 2 (Sulzer SMX, diameter 6 mm, length to diameter ratio L/D = 10) at 121.44°C and from storage tank 3 (1.49 kg/h; Pump 3: mzr-7255 ring gear pump from HNP) mixed with 1,6-hexamethylene diisocyanate. This mixture is then fed into the reactor 2 (model: CSE-X/8G, Form G, inner diameter = 21.0 mm, length = 1500 mm, available from Fluitec), which has been heated to 182°C. The residence time in the reactor 2 is 6.5 min. The pipelines from Reactor 1 to Reactor 2 and from Mixer 2 are slightly heated to about 180°C. The temperature increase in this second heat transfer unit is 37.93°C. The average heat temperature in the inflow to the first reactor was 25°C. The heat temperature during the second HDI addition was 121.44°C, and its c _p (HDI 2) = 1750.27 J/(kg∙K) and c _p (oligomer) = 2000.00 J/(kg∙K). The product has a complex viscosity of 0.15 Pa s at 10 Hz and 190°C. The average OH functionality is 2.

。該平均聚合度 n = 4。The ratio of the NCO groups in the polyisocyanate monomer to the hydroxyl groups in the polyol monomer

. The average degree of polymerization n=4.

The allophanate content is 0.35%.

為4389 g/mol，

為1677 g/mol，因此該比例為2.62。測定

為8095 g/mol，因此該比例為

=1.84。Determination

Is 4389 g/mol,

Is 1677 g/mol, so the ratio is 2.62. Determination

Is 8095 g/mol, so the ratio is

=1.84.

The melting point is 173°C.

The heat dissipated in the tubular reactor is about 55% of the heat used.

Non-invention embodiment:

A Teflon beaker equipped with a stirrer was filled with 35.11 g of butane-1,4-diol, covered with nitrogen and heated to approximately 180°C. Then 55.02 g of HDI was added dropwise with stirring, so that the temperature of the reaction mixture did not exceed 200°C (approximately 45 min). This is accompanied by a significant increase in the viscosity of the mixture. Then the remaining 9.71 g of HDI was added and the reaction mixture was stirred for another 30 min to complete the reaction of the HDI. This was accompanied by a gradual increase in temperature to 211°C and a further increase in viscosity. The product was then cooled to room temperature and measured. The allophanate content is 1.2%. However, the presence of DMSO-d6 insoluble gel particles (crosslinked) in this sample indicates that the allophanate content is still relatively high. Due to the gel particle factor, GPC is not performed.

(A): Polyisocyanate flow (B): Polyol flow (C): Mixture flow (D): Circulating flow (E): Pre-polymer logistics (1): Polyisocyanate storage container (2): The first feeding device (3): The first mass flow meter (4): Polyol storage container (5): The second feeding device (6): The second mass flow meter (7): The first mixing device (8): The second mixing device (9): Temperature-controllable mixing device (10): Temperature-controlled feeding device (11): The first contact (12): Pressure control valve (13): Three-way valve (14): Collection container (15): Exhaust device (16): Extruder (17): Cooling device (18): Crushing device (19): Polyisocyanate pipeline (20): Polyol pipeline (21): Second contact (22): Circulating feed line (23): The first contact (24): Circulation pipeline (25): Prepolymer feed line

Hereinafter, the present invention will be explained in more detail with reference to FIGS. 1, 2 and 3. In these schemes: Figure 1 shows a preferred device for performing the method of the present invention, Figure 2 shows a further preferred device for performing the method of the present invention, Figure 3 shows a further preferred device for performing the method of the present invention.

without

(A): Polyisocyanate flow

(B): Polyol flow

(C): Mixture flow

(D): Circulating flow

(E): Pre-polymer logistics

(1): Polyisocyanate storage container

(2): The first feeding device

(3): The first mass flow meter

(4): Polyol storage container

(5): The second feeding device

(6): The second mass flow meter

(7): The first mixing device

(8): The second mixing device

(9): Temperature-controllable mixing device

(10): Temperature-controlled feeding device

(11): The first contact

(12): Pressure control valve

(14): Collection container

(20): Polyol pipeline

(21): Second contact

(22): Circulating feed line

(23): The first contact

(24): Circulation pipeline

(25): Prepolymer feed line

Claims (16)

A hydroxyl-terminated polyurethane prepolymer, which is characterized in that the hydroxyl-terminated polyurethane prepolymer is composed of at least 90% by weight of 1,6-diisocyanate hexamethylene The composition of the reaction product of methyl ester and butane-1,4-diol, which is based on the total mass of the hydroxyl-terminated polyurethane prepolymer, and is composed of the hydroxyl-terminated polyurethane prepolymer. The allophanate content of the acid ester prepolymer is ≤ 1.00 mol%, which is based on the combination of all the urethane and allophanate groups in the hydroxyl-terminated polyurethane prepolymer. The sum is used as the basis and measured by NMR spectroscopy in each case. The hydroxyl-terminated polyurethane prepolymer according to claim 1, characterized in that the average degree of polymerization of the hydroxyl-terminated polyurethane prepolymer

In the range from 1.5 to 19, preferably in the range from 2 to 9, and more preferably in the range from 3.2 to 6, the average degree of polymerization is

,in

It is the ratio of the NCO groups in the polyisocyanate monomer to the hydroxyl groups in the polyol monomer. According to claim 1 or 2, the hydroxyl-terminated polyurethane prepolymer is characterized in that the hydroxyl-terminated polyurethane prepolymer is at least 96% by weight, preferably to a certain extent. It is from at least 97% by weight, more preferably from at least 98% by weight to a certain extent, even more preferably from at least 99% by weight to a certain extent, even more preferably from at least 99.5% by weight to a certain extent, and most preferably one To a certain extent, it is composed of at least 99.9% by weight of the reaction product of 1,6-hexamethylene diisocyanate and butane-1,4-diol, which is the hydroxyl-terminated polyurethane pre The total mass of the polymer is the benchmark. The hydroxyl-terminated polyurethane prepolymer according to any one of claims 1 to 3, characterized in that the urethane content of the hydroxyl-terminated polyurethane prepolymer is less than 0.25 mol% to 1.00 mol%, preferably from 0.25 mol% to 0.80 mol%, more preferably from 0.30 mol% to 0.80 mol%, even more preferably from 0.30 mol% to 0.75 mol%, even better than the range from 0.34 mol% to 0.70 mol%, which is based on all the urethane and urea in the hydroxyl-terminated polyurethane prepolymer The sum of the formate groups is the basis, which is determined by NMR spectroscopy. The hydroxyl-terminated polyurethane prepolymer according to any one of claims 1 to 4, characterized in that the hydroxyl-terminated polyurethane prepolymer has the functionality of the monomer The calculated average OH functionality is 1.8 to 2.1, preferably 1.95 to 2.05, more preferably 1.97 to 2.0, most preferably 1.975 to 2.0. The hydroxyl-terminated polyurethane prepolymer according to any one of claims 1 to 5, characterized in that the proportion of the hydroxyl-terminated polyurethane prepolymer

/

In the range from 2 to 20, preferably in the range from 2.5 to 15, more preferably in the range from 4 to 10, where

Is the number-the average molar mass and

It is the mass-average molar mass. In each case, by gel permeation chromatography, the sample is dissolved in a solution of potassium trifluoroacetate in hexafluoroisopropanol ^{with a concentration of 2 mg/cm 3 and polymethyl is used} Determination of methyl acrylate standards. The hydroxyl-terminated polyurethane prepolymer according to any one of claims 1 to 6, characterized in that the hydroxyl-terminated polyurethane prepolymer has a melting point of> 150°C, preferably The melting point is> 160°C, more preferably the melting point is in the range from 165°C to 190°C, which is measured by differential scanning calorimetry in accordance with DIN EN 61006 (November 2004). A method for producing a hydroxyl-terminated polyurethane prepolymer according to any one of claims 1 to 7, characterized in that at least 1,6-hexamethylene diisocyanate and butane-1 , 4-diol reaction, optionally in the presence of catalysts and/or additives and additives, the molar NCO/OH ratio is in the range from 0.6:1.0 to 0.95:1.0. The method according to claim 8, characterized in that the reaction is carried out in a tubular reactor, preferably in a loop reactor or in a static mixer, the tubular reactor having at least one continuous heat conduction In the transfer unit, the heat conducted away preferably totals from 10% to 90%, more preferably from 20% to 70%, particularly preferably from 25% to 60% of the total reaction enthalpy released in the tubular reactor. The method according to claim 8 or 9, characterized in that the method is solvent-free. A composition comprising at least one hydroxy-terminated polyurethane prepolymer according to any one of claims 1 to 7 and butane-1,4-diol, in the composition The amount of alkane-1,4-diol is preferably in the range from 0.05% by weight to 12% by weight, more preferably in the range from 0.35% by weight to 9% by weight, particularly preferably from 0.75% by weight to 6 Within the range of% by weight, the total mass of the composition is used as a reference in each case. A composition comprising at least one hydroxy-terminated polyurethane prepolymer according to any one of claims 1 to 7 and at least one additive. A hydroxyl-terminated polyurethane prepolymer according to any one of claims 1 to 7 or a composition according to claim 11 or 12 for use in thermoplastic polyurethane and/or thermoplastic polyamine Use for the manufacture of formate dispersions. A polymer obtained by combining at least one hydroxyl-terminated polyurethane prepolymer according to any one of claims 1 to 7 or a composition according to claims 11 or 12 and at least one chain extender Obtained or obtainable by reaction, the chain extender is preferably a polyisocyanate. An article which contains or contains the polymer according to claim 14, the prepolymer according to any one of claims 1 to 7, or the composition according to claim 11 or 12. A use of the polymer according to claim 14 for the manufacture of molded articles, films and/or fibers.

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